CN115010729A - 一种具有聚集诱导发光效应的稀土荧光材料及其制备方法和应用 - Google Patents
一种具有聚集诱导发光效应的稀土荧光材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种具有聚集诱导发光效应的稀土荧光材料及其制备方法和应用,所述稀土荧光材料包括摩尔比为4:2:1的环丙沙星、鸟苷一磷酸和稀土铕离子,以环丙沙星和鸟苷一磷酸为配体、铕离子为金属中心体在室温水相中通过自组装反应形成配合物CIP‑Eu‑AMP。本发明在室温水相中制备了具有聚集诱导发光效应的稀土荧光材料,制备过程快速、简便、绿色,未涉及有毒有害有机溶剂以及高温下合成反应。该材料中配体对稀土离子Eu3+荧光具有较高的敏化效率,可显著增强Eu3+的特征荧光,有望应用于环境或生物样品中目标物的分析测定,不易受背景荧光的干扰。
Description
技术领域
本发明属于环境功能材料领域,具体涉及一种具有聚集诱导发光效应的稀土荧光材料及其制备方法和应用。
背景技术
基于聚集诱导发射(AIE)的荧光材料在分散良好时几乎没有发射,但在高浓度溶液中聚集或组装后其荧光显著增强,其光稳定性、灵敏性等特点在生物标记与示踪、生物样品检测、细胞成像等方面具有显著优势。基于稀土元素(Ln) 的光学探针具有独特的发光特性,即大斯托克斯位移、尖锐的线状发射带、耐光漂白和长荧光寿命(微秒到毫秒)等,尤其是铕(Eu)和铽(Tb)作为金属节点的稀土配合物材料,可以有效避免生物或环境样品中背景荧光的干扰,进一步提高检测精度。然而大多数稀土发光材料荧光量子产率较低,从而限制了其进一步推广应用。因此,制备具有聚集诱导发光效应的稀土荧光材料是一项具有挑战与有意义的研究工作。
发明内容
针对现有技术的不足,本发明提供一种具有聚集诱导发光效应的稀土荧光材料及其制备方法和应用,是一种聚集诱导稀土发光材料的快速水相合成方法,可用于生物与环境样品分析、污染物去除等。
本发明是通过以下技术方案实现的:
一种具有聚集诱导发光效应的稀土荧光材料,包括摩尔比为4:2:1的环丙沙星、鸟苷一磷酸和稀土铕离子,以环丙沙星和鸟苷一磷酸为配体、铕离子为金属中心体在室温水相中通过自组装反应形成配合物CIP-Eu-AMP;所述 CIP-Eu-AMP具有如式Ⅰ所示的结构式:
一种具有聚集诱导发光效应的稀土荧光材料的制备方法,包括以下步骤:
步骤1)在9mL去离子水中加入环丙沙星和鸟苷一磷酸,超声处理30min 后,加入1mL Tris-HCl缓冲溶液并将溶液在室温下搅拌1h,得到混合溶液;
步骤2)将500μL铕离子溶液逐滴加入到步骤1)制得的混合溶液中,在室温下继续搅拌30min后,向溶液中缓慢滴加100μL NaOH标准溶液,在室温下搅拌6h形成凝胶状溶液;
步骤3)通过冷冻干燥获得CIP-Eu-AMP粉末,即得。
优选地,步骤1)所述环丙沙星和鸟苷一磷酸的摩尔浓度比为2:1。
优选地,步骤1)所述Tris-HCl缓冲溶液的浓度为200mM,pH=8.0。
优选地,步骤2)所述铕离子溶液的浓度为100mM。
优选地,步骤2)所述NaOH标准溶液的浓度为3M。
一种具有聚集诱导发光效应的稀土荧光材料在生物与环境样品分析中的应用。
一种具有聚集诱导发光效应的稀土荧光材料在污染物去除中的应用。
本发明的有益效果如下:
本发明在室温水相中制备了具有聚集诱导发光效应的稀土荧光材料,制备过程快速、简便、绿色,未涉及有毒有害有机溶剂以及高温下合成反应;相对于现有的稀土发光材料,该材料中配体对稀土离子Eu3+荧光具有较高的敏化效率,可显著增强Eu3+的特征荧光,使其荧光量子产率高达23.03%;基于Eu3+的特征红色荧光,该荧光材料有望应用于环境或生物样品中目标物的分析测定,不易受背景荧光的干扰。
附图说明
图1为实施例2中利用不同摩尔浓度比的CIP和AMP(MCIP/MAMP)制备得到的CIP-Eu-AMP溶液照片(A)以及其静置24h之后的照片(B);
图2为实施例3中:A为CIP-Eu-AMP(a)和AMP-Eu(b)溶液照片;B 为CIP-Eu-AMP(a)和AMP-Eu(b)溶液在静置24h后的照片;
图3为实施例3中:A为CIP-Eu-AMP的扫描电镜图片,B为AMP-Eu的扫描电镜图片,比例尺为200nm;C为CIP-Eu-AMP的能量色散谱图;
图4为实施例3中:A为CIP-Eu-AMP(a)和AMP-Eu(b)的XRD图谱;B为CIP(a)、AMP(b)、CIP-Eu-AMP(c)的FT-IR光谱;C为CIP-Eu-AMP 的XPS全谱图;
图5为实施例4中:A为不同体系的激发光谱和发射光谱;B为不同浓度 CIP-Eu-AMP的荧光光谱图;C为CIP-Eu-AMP在416nm处的荧光寿命衰减曲线;D为CIP-Eu-AMP在613nm处的荧光寿命衰减曲线;
图6为实施例4中CIP-Eu-AMP的紫外吸收光谱;
图7为实施例4中0.1g·L-1(A)和0.5g·L-1(B)的CIP-Eu-AMP溶液的水合粒径分布图。
具体实施方式
下面结合附图与具体实施例对本发明做进一步详细说明。
实施例1CIP-Eu-AMP的制备
一种具有聚集诱导发光效应的稀土荧光材料,以环丙沙星(CIP)和鸟苷一磷酸(AMP)为配体、Eu3+为金属中心体在室温水相中通过自组装反应形成配合物CIP-Eu-AMP,其中,CIP、AMP和Eu3+三者的摩尔比为4:2:1。
所述CIP-Eu-AMP的结构式如下式Ⅰ所示:
一种具有聚集诱导发光效应的稀土荧光材料的制备方法,具体步骤如下:
(1)在9mL去离子水中加入CIP(0.2mmol,73mg)和AMP(0.1mmol, 36.8mg),超声处理30min后,加入1mL Tris-HCl缓冲溶液(200mM,pH=8.0) 并将溶液在室温下搅拌1h,得到混合溶液。
(2)将500μL Eu3+溶液(100mM)逐滴加入到上述混合溶液中。在室温下继续搅拌30min后,向溶液中缓慢滴加100μL NaOH标准溶液(3M),在室温下搅拌6h形成凝胶状溶液。
(3)最后通过冷冻干燥获得CIP-Eu-AMP粉末,用于进一步表征。
实施例2CIP-Eu-AMP合成条件的优化
研究了用不同摩尔浓度比的CIP和AMP(MCIP/MAMP)制备的CIP-Eu-AMP。如图1所示,只有MCIP/MAMP为2:1时,形成的CIP-Eu-AMP呈透明均质胶体,并具有最强的Eu3+特征红色荧光,而利用其他MCIP/MAMP的CIP和AMP制备的 CIP-Eu-AMP溶液浑浊且在静置12h后产生明显沉淀。
实施例3CIP-Eu-AMP的表征
按照实施例1的方法制备CIP-Eu-AMP和AMP-Eu溶液,其中AMP-Eu溶液的制备除了未引入CIP,其他操作过程与CIP-Eu-AMP一致。
如图2所示,图2A为制备的CIP-Eu-AMP(a)和AMP-Eu(b)溶液照片;图2B为CIP-Eu-AMP(a)和AMP-Eu(b)溶液在静置24h后的照片。与浑浊的AMP-Eu溶液不同,CIP-Eu-AMP溶液呈现凝胶状;此外,由于CIP-Eu-AMP 呈均质胶体状,长时间放置后仍然分散均匀。
通过扫描电子显微镜(SEM)对制备的CIP-Eu-AMP和AMP-Eu形态进行表征,如图3A、图3B所示,相互粘附的CIP-Eu-AMP纳米颗粒呈现直径约300 nm的均一棒状形态(图3A),而AMP-Eu呈现直径小于50nm的聚集纳米颗粒球体(图3B)。该结果表明CIP参与了AMP-Eu中的配位,形成了更大尺寸且形貌规则均一的纳米颗粒。通过元素分布图和能量色散谱图对CIP-Eu-AMP的元素组成及含量进行了表征,如图3C所示。结果表明,CIP-Eu-AMP中可观察到C、 N、O、F、P和Eu六种元素的分布,且F、P和Eu的重量百分比分别为2.6%、 0.5%和2.1%,揭示了CIP、AMP和Eu3+都参与了CIP-Eu-AMP的构筑。
CIP-Eu-AMP(图4A曲线a)和AMP-Eu(图4A曲线b)的X射线衍射(XRD) 图谱如图4A所示,结果表明两者均没有明显的特征衍射峰,表明它们的无定形结构。
此外,通过傅里叶变换红外光谱(FT-IR)进一步证实了CIP-Eu-AMP聚合物的成功制备,对CIP、AMP和CIP-Eu-AMP的FT-IR光谱表征结果如图4B所示。在CIP中(图4B曲线a),1630、1460、1389cm-1处的吸收带分别代表C=O、 asym(COO)和sym(COO)的特征伸缩振动,1272cm-1处的吸收峰代表C-F 的伸缩振动;在CIP-Eu-AMP中(图4B曲线c),观察到了C-F伸缩振动的吸收带,而C=O的吸收峰移动到了1610cm-1,asym(COO)的吸收峰从1460cm-1蓝移到了1480cm-1,该结果表明了CIP和Eu3+的配位结合。在AMP中(图4B 曲线b),1040cm-1处代表磷酸基团的特征吸收带,在1460和1600cm-1处的吸收峰分别代表C-O和C-N伸缩振动。与AMP光谱相比,CIP-Eu-AMP中磷酸基团的吸收带红移至1030cm-1,与C-N相关的特征伸缩带红移至1580cm-1。
此外,通过X射线光电子能谱(XPS)对CIP-Eu-AMP的表面元素组成进行了表征,结果如图4C所示。在130.6、285.0、399.1、531.2、686.0eV处结合能峰分别代表P 2p、C 1s、N1s、O 1s和F1s,1127.2和1156.1eV代表Eu 3d的结合能峰。上述表现结果表明,以CIP和AMP作为配体、Eu3+为金属中心体成功自组装得到CIP-Eu-AMP聚合物。
实施例4CIP-Eu-AMP的光学性质
对CIP-Eu-AMP的聚集诱导发光特性进行了表征研究。
如图5A所示,CIP中的N和O原子与Eu3+配位后,其在416nm处的荧光发射降低,但没有观察到Eu3+的特征发射峰,表明CIP和Eu3+之间的天线效应较弱,即CIP不能有效向Eu3+进行能量转移敏化其发光。AMP是制备配位聚合物的理想配体之一,因为它的核碱基部分和磷酸基团为Ln离子提供了极好的结合位点,因此当AMP遇到Eu3+时可以形成白色聚合物,但是AMP-Eu体系未观察到Eu3+的特征荧光。而将CIP和AMP作为双配体、Eu3+为金属中心体通过自组装制备的CIP-Eu-AMP均质胶体,在365nm紫外光下可观察到强Eu3+特征红色荧光,并且CIP在416nm的发射荧光几乎完全淬火。
为了进一步证明AIE发光机制,研究了不同浓度CIP-Eu-AMP的荧光光谱和荧光寿命衰减曲线。如图5B所示,随着CIP-Eu-AMP浓度的增加,Eu3+荧光逐渐增强,同时CIP荧光随之减弱,CIP-Eu-AMP体系荧光颜色由蓝色逐渐变为红色。CIP-Eu-AMP体系在613nm和416nm处的荧光寿命曲线表征结果如图5C 和图5D所示,随着CIP-Eu-AMP浓度从0.1g·L-1增加到0.5g·L-1,Eu3+的荧光寿命从273μs增加到1018μs,CIP的荧光寿命从12.1ns降低到8.9ns。这是由于CIP-Eu-AMP浓度的增加导致其中纳米颗粒的团聚,减少了配体与Eu3+之间的距离,并限制了配体的分子内振动和旋转,从而增强CIP向Eu3+的能量转移,导致Eu3+的荧光寿命增加和CIP的荧光寿命降低。但是,当CIP-Eu-AMP浓度高于0.5g·L-1时,CIP荧光持续降低,而Eu3+的发射强度和荧光寿命也略有下降。造成这种现象的原因可能是浓度过高的CIP-Eu-AMP进一步聚集成具有更大尺寸的颗粒,使其表面积减小,进而导致其对紫外光的吸收减少,Eu3+荧光减弱。如图6所示,当CIP-Eu-AMP浓度低于0.5g·L-1时,CIP-Eu-AMP对紫外光的吸光强度逐渐增加;当其浓度高于0.5g·L-1时,吸光强度下降。
此外,通过动态光散射分析(DLS)获得了不同浓度CIP-Eu-AMP的水合粒径尺寸分布,以证明其聚集状态尺寸的增大。如图7A、图7B所示,0.1g·L-1 CIP-Eu-AMP的水合粒径平均尺寸为8.9±0.5nm,在0.5g·L-1的浓度下增加到 130.7±0.8nm,而在0.05g·L-1CIP-Eu-AMP溶液体系中未检测到DLS信号,且当浓度达到2.0g·L-1时,CIP-Eu-AMP的水合粒径平均尺寸增加到389.6±1.2nm,表明高浓度体系中的聚集状态。
此外,0.5g·L-1CIP-Eu-AMP体系中可观察到丁达尔效应,而在0.1g·L-1的浓度下没有观察到丁达尔效应。
以上表征结果证实了随着CIP-Eu-AMP浓度的增加,CIP-Eu-AMP聚集成更大尺寸的胶体颗粒,且Eu3+在613nm处的特征荧光逐渐增强,这是典型AIE机制特征。
以上所述仅为本发明的较佳实施例而已,并非对本发明做任何形式上的限定。凡本领域技术人员利用本发明的技术方案对上述实施例作出的任何等同的变动、修饰或演变等,均仍属于本发明技术方案的范围内。
Claims (8)
2.权利要求1所述的一种具有聚集诱导发光效应的稀土荧光材料的制备方法,其特征在于,包括以下步骤:
步骤1)在9mL去离子水中加入环丙沙星和鸟苷一磷酸,超声处理30min后,加入1mLTris-HCl缓冲溶液并将溶液在室温下搅拌1h,得到混合溶液;
步骤2)将500μL铕离子溶液逐滴加入到步骤1)制得的混合溶液中,在室温下继续搅拌30min后,向溶液中缓慢滴加100μL NaOH标准溶液,在室温下搅拌6h形成凝胶状溶液;
步骤3)通过冷冻干燥获得CIP-Eu-AMP粉末,即得。
3.根据权利要求2所述的一种具有聚集诱导发光效应的稀土荧光材料的制备方法,其特征在于,步骤1)所述环丙沙星和鸟苷一磷酸的摩尔浓度比为2:1。
4.根据权利要求2所述的一种具有聚集诱导发光效应的稀土荧光材料的制备方法,其特征在于,步骤1)所述Tris-HCl缓冲溶液的浓度为200mM,pH=8.0。
5.根据权利要求2所述的一种具有聚集诱导发光效应的稀土荧光材料的制备方法,其特征在于,步骤2)所述铕离子溶液的浓度为100mM。
6.根据权利要求2所述的一种具有聚集诱导发光效应的稀土荧光材料的制备方法,其特征在于,步骤2)所述NaOH标准溶液的浓度为3M。
7.权利要求1所述的一种具有聚集诱导发光效应的稀土荧光材料在生物与环境样品分析中的应用。
8.权利要求1所述的一种具有聚集诱导发光效应的稀土荧光材料在污染物去除中的应用。
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